JP6205297B2 - Water-in-oil emulsified cosmetic - Google Patents

Description

  The present invention relates to a water-in-oil emulsified cosmetic.

Make-up products such as foundations and sun care products are required not only to have sunscreen effects but also to be resistant to sweat and sebum. However, since the water-in-oil type dosage form has an oil-based outer phase, the oil-specific stickiness may be felt strongly.
Silicone oil is often used as an oil agent in order to provide a refreshing and non-sticky feeling and to improve the longevity of makeup.
However, silicone oils have poor compatibility with other cosmetic oils such as hydrocarbons and ester oils, making it difficult to uniformly emulsify, and problems with stability over time such as viscosity reduction and separation occur.
A cleansing milk containing di (caprylic acid / capric acid) propanediol is disclosed (Patent Document 1).
A water-in-oil emulsified sunscreen cosmetic that contains caprylyl methicone and specific zinc oxide, volatile silicone, lipophilic active agent, and organically modified clay mineral and that has excellent cosmetic durability and cleanability is disclosed (patent) Reference 2). A sunscreen cosmetic containing caprylyl methicone, a silicone resin and a sunscreen is disclosed (Patent Document 3). A water-in-oil type emulsion sunscreen cosmetic containing caprylyl methicone, an ultraviolet absorber and a dextrin fatty acid ester is disclosed (Patent Document 4). A cosmetic containing caprylyl methicone and a fluorine-modified silicone resin has been disclosed (Patent Document 5).
An oily skin external preparation containing a composite powder in which the surface of a silicone resin-coated silicone rubber powder is coated with zinc oxide and an oil component is disclosed (Patent Document 6). An external composition containing a specific silicone resin-coated rubber powder, siliconeized pullulan, and silicone oil has been disclosed (Patent Document 7). A water-in-oil emulsified cosmetic containing a silicone resin-coated silicone rubber powder, a volatile oil, a nonvolatile oil, and an aqueous phase is disclosed (Patent Document 8).

JP 2014-028762 A Japanese Patent No. 4596449 Japanese Patent No. 5336362 JP 2011-126732 A JP 2003226663 A JP 2004-217621 A Japanese Patent No. 3689588 Japanese Patent No. 4315878

Organically modified clay minerals are widely used as an emulsifier suitable for water-in-oil emulsification of silicone oil. However, there is a problem that the viscosity decreases with time.
In order to increase the viscosity, a dextrin fatty acid ester is blended, but even when a dextrin fatty acid ester is blended, the clay lowering with time is not sufficiently solved.
Therefore, a water-in-oil emulsified cosmetic blended with an organically modified clay mineral and a dextrin fatty acid ester has a predetermined viscosity of, for example, 20,000 mPa · s or more, suppresses a decrease in viscosity over time, and gives a feeling of use (extended ), And to provide a preparation excellent in ultraviolet shielding effect. As a result of diligent investigation of additive components such as oils and powders to solve the problem, surprisingly, di (caprylic acid / capric acid) propanediol, caprylyl methicone and silicone resin-coated silicone rubber spherical powder were blended at the same time. As a result, the present inventors have found that the problem can be solved and completed the present invention.

That is, the present invention has the following configuration.
[1] A water-in-oil emulsified cosmetic comprising di (caprylic acid / capric acid) propanediol, caprylyl methicone and silicone resin-coated silicone rubber spherical powder.
[2] The water-in-oil emulsified cosmetic according to [1], comprising a dextrin fatty acid ester and an organically modified clay mineral.
[3] The water-in-oil emulsified cosmetic according to [1] or [2], comprising a metal oxide.

  According to the present invention, it was possible to provide a water-in-oil emulsified cosmetic that has a certain viscosity, suppresses a decrease in viscosity over time, and has an excellent feeling of use (freeness) and an ultraviolet shielding effect. . In particular, for water-in-oil type emulsified cosmetics containing organically modified clay minerals and dextrin fatty acid esters, it was possible to provide cosmetics having the above effects.

It is a graph which shows the time-dependent stability (0 day after adjustment, 1 day, 7 days, 14 days, 28 days) of the emulsification-in-oil cosmetic in each composition.

The di (caprylic / capric) propanediol used in the present invention is a diester of 1,3-propanediol and a mixed fatty acid composed of caprylic acid and capric acid. A commercially available product can be used as di (caprylic acid / capric acid) propanediol. As a commercial item, Nisshin Oilio Group Saracos PR-85 is mentioned.
The blending amount of di (caprylic acid / capric acid) propanediol used in the present invention is preferably 0.5% by mass or more and 5% by mass or less. If the amount is less than 0.5% by mass, the effect may be insufficient, and even if the amount exceeds 5% by mass, the effect cannot be expected to increase.

Caprylyl methicone used in the present invention is a kind of alkyl-modified trisiloxane, and one of the two methyl groups bonded to the second (center) silicon atom of the trisiloxane skeleton is a caprylyl group (n-octyl group). ). A commercial item can be used for caprylyl methicone. Commercially available products include Toray Dow Corning SS-3408 and Momentive Performance Materials SILSOFT034.
The blending amount of caprylyl methicone used in the present invention is preferably 0.3% by mass or more and 5% by mass or less. If the amount is less than 0.3% by mass, the effect may be insufficient, and even if the amount exceeds 5% by mass, the effect cannot be expected to increase.

The silicone resin-coated silicone rubber spherical powder used in the present invention is a composite powder whose cosmetic label is specified by “polysilicone-1 crosspolymer”, and is a copolymer of dimethicone, hydrogen dimethicone, and silsesquioxane. Is crosslinked with bisvinyldimethicone. A commercially available product can be used as the silicone resin-coated silicone rubber spherical powder. A commercially available product is KSP-411 manufactured by Shin-Etsu Chemical Co., Ltd.
The blending amount of the silicone resin-coated silicone rubber spherical powder used in the present invention is preferably 0.5% by mass or more and 5% by mass or less. If the amount is less than 0.5% by mass, the effect may be insufficient, and even if the amount exceeds 5% by mass, the effect cannot be expected to increase.

A dextrin fatty acid ester can be blended in the water-in-oil emulsified cosmetic of the present invention. Examples of dextrin fatty acid esters include dextrin palmitate, (palmitic acid / 2-ethylhexanoic acid) dextrin, dextrin myristate, and the like.
The amount of the dextrin fatty acid ester used in the present invention is preferably 0.1% by mass or more and 5% by mass or less. If it is less than 0.1% by mass, the effect may be insufficient, and even if it exceeds 5% by mass, it cannot be expected that the effect will be further enhanced.

An organically modified clay mineral can be blended in the water-in-oil emulsified cosmetic of the present invention. Smectite, which is a swellable layered silicate, is a cationic clay mineral, and a material obtained by replacing the cation with an organic cation such as a quaternary ammonium salt is called an organically modified clay mineral. Examples of minerals contained in smectite include hectorite, montmorillonite, bentonite, saponite, beidellite, nontronite, stevensite, vermiculite, bolconskite, soconite, magadite, and Kenyalite. Examples of the organic cation include dimethyl distearyl ammonium chloride, dimethyl dipalmityl ammonium chloride, stearyl benzyl dimethyl ammonium chloride, stearyl trimethyl ammonium chloride, and lauryl dimethylaminoacetic acid betaine. Examples of the organically modified clay mineral include disteardimonium hectorite, stearalkonium hectorite, stearalkonium bentonite and the like.
The blending amount of the organically modified clay mineral used in the present invention is preferably 0.1% by mass or more and 5% by mass or less. If it is less than 0.1% by mass, the effect may be insufficient, and even if it exceeds 5% by mass, it cannot be expected that the effect will be further enhanced.
When an organically modified clay mineral is blended, there is a problem that the viscosity decreases with time, but according to the present invention, the viscosity has such a predetermined viscosity, the decrease in viscosity with time is suppressed, and the viscosity is stably maintained. can do. The predetermined viscosity is preferably 15,000 mPa · s or more, and more preferably 20,000 mPa · s or more.
Further, as the stability over time, the decrease rate after 2 weeks is preferably less than 20%, more preferably the decrease rate after 3 weeks is preferably less than 20%, and the decrease rate after 4 weeks. It is even more desirable that is less than 20%.

  A metal oxide can be mix | blended with the water-in-oil type emulsion cosmetics of this invention. In order to impart an ultraviolet shielding effect, it is preferable to incorporate a fine particle metal oxide such as fine particle titanium oxide, fine particle zinc oxide, fine particle cerium oxide. What is necessary is just to select the thing of the various particle diameter and shape which can be obtained as a particulate metal oxide according to the objective. For example, titanium oxide is granular, needle-like, spindle-shaped, plate-like, flake-like, etc., zinc oxide is spherical or plate-like hexagonal, and cerium oxide is A spherical thing can be used suitably. Further, the same substances having different particle sizes and shapes may be used in combination, or two or more substances may be used in arbitrary combination.

  As the fine particle metal oxide, those having an average primary particle diameter of 1 nm to 100 nm, more preferably 5 to 50 nm are suitably used.

  When the average particle diameter of the primary particles of the fine particle metal oxide is larger than 100 nm, the scattering of the particles with respect to the visible light increases, so that the transmittance of visible light, that is, the transparency is lowered.

  In order to reduce the surface activity of the particulate metal oxide, those whose surface is coated with silica, aluminum hydroxide or the like are preferably used.

  Furthermore, in order to improve the dispersibility of the fine particle metal oxide in the oil component, it is possible to preferably use a part or all of the surface treated with a hydrophobizing agent. Examples of the hydrophobizing surface treatment agent include silicone treatment agents, fatty acids, fatty acid soaps, and fatty acid esters. Examples of the silicone treating agent include various silicone oils such as methyl hydrogen polysiloxane, dimethyl polysiloxane, and methylphenyl polysiloxane, methyltrimethoxysilane, ethyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, and the like. And various fluoroalkylsilanes such as trifluoromethylethyltrimethoxysilane and heptadecafluorodecyltrimethoxysilane. Examples of the fatty acid include palmitic acid, isostearic acid, stearic acid, lauric acid, myristic acid, behenic acid, oleic acid, rosin acid, 12-hydroxystearic acid and the like. Examples of the fatty acid soap include aluminum stearate, calcium stearate, and 12-hydroxyaluminum stearate. Examples of the fatty acid ester include dextrin fatty acid ester, cholesterol fatty acid ester, sucrose fatty acid ester, starch fatty acid ester and the like. These are generally used for the hydrophobizing treatment of fine particle metal oxides in the preparation of cosmetics, and are not particularly limited, but methylpolysiloxane treatment, methylhydrogenpolysiloxane treatment are not limited. Preferably used.

  The blending amount of the particulate metal oxide in the water-in-oil emulsified cosmetic of the present invention may be appropriately set based on the kind of particulate metal oxide, desired ultraviolet shielding property, etc., and is not particularly limited. 1 to 30% by weight of the emulsified cosmetic, more preferably 5 to 20% by weight.

  The water-in-oil emulsified cosmetic of the present invention includes fats and oils such as ester oils and vegetable oils, hydrocarbons, higher fatty acids, higher alcohols, silicone oils, anionic surfactants, cationic surfactants, and amphoteric surfactants. , Nonionic surfactants, polyhydric alcohols, saccharides, sugar alcohols, water-soluble polymers, thickeners, preservatives, sequestering agents, UV absorbers, moisturizers such as hyaluronic acid, perfume, pH A regulator, etc. can be contained. Other medicinal components such as vitamins, skin activators, blood circulation promoters, active oxygen scavengers, anti-inflammatory agents, whitening agents, bactericides, and physiologically active components can also be contained.

Examples of ester oils include octyldodecyl stearoyloxystearate, cetyl 2-ethylhexanoate, 1,3-butylene glycol diisononanoate, 1,3-butylene glycol di-2-ethylhexanoate, dipropylene glycol diisononanoate, di-2 -Dipropylene glycol ethylhexanoate, isononyl isononanoate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, glyceryl triisostearate, neopentyl glycol dicaprate, and the like.
As fats and oils, for example, camellia oil, evening primrose oil, macadamia nut oil, olive oil, rapeseed oil, corn oil, sesame oil, jojoba oil, germ oil, wheat germ oil, etc. liquid fats and oils, cacao butter, coconut oil, hardened coconut oil, Solid oils such as palm oil, palm kernel oil, owl, owl kernel oil, hydrogenated oil, hydrogenated castor oil, waxes such as beeswax, candelilla wax, cotton wax, nuka wax, lanolin, lanolin acetate, liquid lanolin, sugarcane wax Can be mentioned.
Examples of hydrocarbons include liquid paraffin, squalene, squalane, and microcrystalline wax.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, docosahexaenoic acid (DHA), eicosapentaenoic acid (EPA), and the like.

Examples of the higher alcohol include linear alcohols such as lauryl alcohol, stearyl alcohol, cetyl alcohol, and cetostearyl alcohol, and branched chain alcohols such as monostearyl glycerol ether, lanolin alcohol, cholesterol, phytosterol, and octyldodecanol.
Examples of the silicone oil include cyclomethicone of cyclic polysiloxane, such as dimethylpolysiloxane of chain polysiloxane, methylphenyl polysiloxane, and the like.

Examples of the anionic surfactant include fatty acid salts such as sodium laurate, higher alkyl sulfates such as sodium lauryl sulfate, alkyl ether sulfates such as POE lauryl sulfate triethanolamine, N-acyl sarcosine acid, sulfosuccinate , N-acyl amino acid salts and the like.
Examples of the cationic surfactant include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, benzalkonium chloride, and benzethonium chloride.
Examples of amphoteric surfactants include betaine surfactants such as alkyl betaines and amide betaines.
Examples of nonionic surfactants include polyglycerin fatty acid esters such as polyglyceryl-2 triisostearate, PEG-9 dimethicone, PEG-10 dimethicone, PEG-9 polydimethylsiloxyethyl dimethicone, PEG / PPG-19 / 19 dimethicone. Silicone surfactants such as sorbitan, sorbitan fatty acid esters such as sorbitan monooleate, and hardened castor oil derivatives.

Examples of the polyhydric alcohols include glycerin, 1,3-butylene glycol, 1,2-pentanediol, propylene glycol, dipropylene glycol, isoprene glycol, polyethylene glycol and the like.
Examples of sugars and sugar alcohols include glucose, fructose, sorbitol, maltitol, erythritol, trehalose, sucrose, xylitol, maltose, and lactose.

Examples of water-soluble polymers include gum arabic, gum tragacanth, galactan, guar gum, carrageenan, pectin, agar, quince seed, dextran, pullulan, carboxymethyl starch, collagen, casein, gelatin, methylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, Examples include sodium carboxymethylcellulose, sodium alginate, carboxyvinyl polymer, and the like.
Examples of the thickener include glyceryl behenate eicosanedioate.

Examples of preservatives include methyl paraben and ethyl paraben.
Examples of the sequestering agent include edetates such as disodium ethylenediaminetetraacetate, edetic acid, and sodium edetate.

  As the ultraviolet absorber, for example, paraaminobenzoic acid, phenyl salicylate, isopropyl paramethoxycinnamate, octyl paramethoxycinnamate, 2,4-dihydroxybenzophenone, and the like can be blended. However, in order to improve safety, it is preferable not to add an ultraviolet absorber.

  Examples of humectants include polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,2-pentanediol, glycerin, diglycerin, polyglycerin, xylitol, maltitol, maltose, sorbitol, glucose, fructose. , Sodium chondroitin sulfate, sodium hyaluronate, sodium lactate, pyrrolidone carboxylic acid, cyclodextrin and the like.

  Examples of medicinal ingredients include vitamin A oil, vitamin A such as retinol, vitamin B2 such as riboflavin, B6 such as pyridoxine hydrochloride, L-ascorbic acid, L-ascorbic acid phosphate, L-ascorbic acid mono Vitamin C such as palmitic acid ester, L-ascorbic acid dipalmitic acid ester, L-ascorbic acid-2-glucoside, pantothenic acid such as calcium pantothenate, vitamin D such as vitamin D2 and cholecalciferol, α-tocopherol And vitamins such as vitamin E such as tocopherol acetate and DL-α-tocopherol nicotinate.

Whitening agents such as glutathione and yukinoshita extract, skin activators such as royal jelly and beech tree extract, blood circulation promoters such as capsaicin, gingeron, cantalis tincture, ictamol, caffeine, tannic acid and γ-oryzanol, glycyrrhizic acid derivatives , Glycyrrhetinic acid derivatives, anti-inflammatory agents such as azulene, amino acids such as arginine, serine, leucine and tryptophan, maltose sucrose condensates of resident bacteria control agents, lysozyme chloride and the like.
In addition, chamomile extract, parsley extract, wine yeast extract, grapefruit extract, honeysuckle extract, rice extract, grape extract, hop extract, rice bran extract, loquat extract, buckwheat extract, yakuinin extract, assembly extract, merilot extract, birch extract, licorice extract, peony extract , Savonso extract, loofah extract, capsicum extract, lemon extract, gentian extract, perilla extract, aloe extract, rosemary extract, sage extract, thyme extract, tea extract, seaweed extract, cucumber extract, carrot extract, carrot extract, maronier extract, Examples include various extracts such as chammel extract and mulberry extract.

The water-in-oil emulsified cosmetic of the present invention comprises di (caprylic acid / capric acid) propanediol, caprylyl methicone and silicone resin-coated silicone rubber spherical powder, and further contains dextrin fatty acid ester, organically modified clay mineral, and metal It is preferable that an oxide is included. The blending amounts of these components are as described above, and more preferable blending examples include the following.
Di (caprylic / capric) propanediol 0.1-1.5% by weight
Caprylyl methicone 0.1-1.5% by weight
Silicone resin-coated silicone rubber spherical powder 0.1 to 2% by weight
Dextrin fatty acid ester 0.1-2% by weight
Organically modified clay mineral 0.1-1% by weight
Metal oxide 5-30% by weight
Moreover, the following is mentioned as a more preferable compounding example.
Di (caprylic acid / capric acid) propanediol 0.5-1.0% by weight
Caprylyl methicone 0.5-1.0% by weight
Silicone resin-coated silicone rubber spherical powder 0.5-1.5 wt%
Dextrin fatty acid ester 0.5-1.5% by weight
Organically modified clay mineral 0.1-0.6% by weight
Metal oxide 15-25% by weight

In the water-in-oil emulsified cosmetic of the present invention, an aqueous phase component is blended together with an oil phase component. The aqueous phase component includes water or an aqueous phase mainly composed of water and various water-soluble components therein. Specifically, an aqueous solution containing sorbitol or sodium chloride in addition to water can be used. The water phase component is desirably blended in an amount of 30 to 60% by weight based on the total amount of the water-in-oil emulsified cosmetic.
If the aqueous phase component is less than 30% by weight, the viscosity may be low and it may be difficult to form a cream. On the other hand, if it exceeds 60% by weight, it is difficult to obtain a water-in-oil emulsion composition.

The method for preparing the water-in-oil emulsified cosmetic of the present invention is performed, for example, as follows.
Silicone resin-coated silicone rubber spherical powder, a part of oil agent, organically modified clay mineral, emulsifier, powder mixed at room temperature, and the remaining oil agent and thickener mixture mixed and dissolved at high temperature are added at high temperature and stirred Mix, cool to room temperature and stir while slowly adding the aqueous phase mixed at room temperature.

  Water-in-oil emulsified cosmetics having the composition shown in Table 1 were prepared. Silicone resin-coated silicone rubber spherical powder (1), oil agent (3), (4), organically modified clay mineral (7), emulsifiers (8) to (12), powder (13) to (17) at room temperature Add and mix the oil agent (2), (5), thickener (6) mixture mixed and dissolved at 90 ° C. with high temperature, stir and mix, and cool to room temperature. The water phases (18) to (20) mixed at room temperature were stirred while being gradually added to prepare a water-in-oil emulsified cosmetic.

(Source of main ingredients)
1 Polysilicone-1 cross polymer: KSP-411 manufactured by Shin-Etsu Chemical Co., Ltd.
2 Di (caprylic acid / capric acid) propanediol: Nisshin Oilio Group Saracos PR-85
3 Caprylyl methicone: SS-3408 manufactured by Toray Dow Corning
6 Dextrin palmitate: Chiba Milling Leopard KL2
7 Disteardimonium hectorite: Nikko Chemical's NIKKOL Nikomulus WO origin

(Evaluation method)
1. Measurement of viscosity Viscosity was measured using a B-type viscometer, rotor No. The measurement was performed under conditions of 4, 12 rpm and 30 seconds.

2. Evaluation of Viscosity on the Day after Preparation Viscosity of 15,000 or more and 30,000 or less was evaluated as “◯”, viscosity of 10,000 or more and less than 15,000 was evaluated as Δ, and viscosity of less than 10,000 was evaluated as ×.

3. Stability of viscosity over time A change in viscosity after 1 month storage at room temperature was evaluated as ○, ± 30% or more and less than 50% as Δ, and ± 50% or more as ×.

4). Usability (free)
Ten expert panelists evaluated “Nobi”. The evaluation criteria were as follows.
Good: 3 points Normal: 2 points Bad: 1 point Based on the above evaluation criteria, the number of expert panelists was tabulated and evaluated according to the following criteria.
23 points or more: ○
18 points or more and 22 points or less: △
17 points or less: ×

5. SPF measurement:
Apply a water-in-oil emulsified cosmetic evenly to a PMMA plate (HelioScreen Laboratoire) at 1.3 mg / cm ² and measure the in-vitro SPF value with SPFAnalyzer UV-2000S (Labsphere). It was.

(Evaluation results)
Example 1 containing di (caprylic acid / capric acid) propanediol, caprylyl methicone and silicone resin-coated silicone rubber spherical powder has a viscosity of 20,000 mPa · s or more, and the viscosity decrease with time is also suppressed. The feeling of use (expansion) was good, and the ultraviolet shielding effect was high.
On the other hand, Comparative Example 1 which does not contain caprylmethicone, Comparative Example 2 which does not contain di (caprylic acid / capric acid) propanediol, and Comparative Example 3 which does not contain a silicone resin-coated silicone rubber spherical powder, After one month, it decreased to about 1/3 or less, and the feeling of use (expansion) and the ultraviolet shielding effect were not satisfactory.

  According to the present invention, it is possible to provide a water-in-oil emulsified cosmetic that has a certain viscosity, suppresses a decrease in viscosity over time, and is excellent in feeling of use (spread) and an ultraviolet shielding effect.

Claims (3)

A water-in-oil emulsified cosmetic comprising di (caprylic / capric) propanediol, caprylyl methicone and silicone resin-coated silicone rubber spherical powder. The water-in-oil emulsified cosmetic according to claim 1, comprising a dextrin fatty acid ester and an organically modified clay mineral. The water-in-oil emulsified cosmetic according to claim 1 or 2, comprising a metal oxide.

Images